Deposition Velocities of SO2 and O3 over Agricultural and Forest Ecosystems

The results of field studies that measured the flux anddeposition velocity of SO₂ and O₃ are reported. Three of the studies were over agricultural crops (pasture, corn, and soybean), and two were over forest (a deciduous forest and a mixed coniferous–deciduous forest). In all cases the deposition velocity for SO₂ was higher than that for O₃. Diurnal cycles of SO₂ deposition velocity were similar in shape, but not magnitude for all surfaces; however those for O₃ showed some difference between forest sites where the peak was in the morning, and the agricultural sites where the peak occurred at mid-day. Seasonal cycles of SO₂ were affected by deposition to surfaces when leaves were not active, yet surface conductance is significant, but not for O₃ where stomatal uptake is the primary pathway for deposition.(On assignment to the National Exposure Research Lab., US EPA) (e-mail:     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

A Coupled Land-Surface and Dry Deposition Model and Comparison to Field Measurements of Surface Heat,Moisture, and Ozone Fluxes

We have developed a coupled land-surface and drydeposition model for realistic treatment of surface fluxes ofheat, moisture, and chemical dry deposition within acomprehensive air quality modelling system. A new land-surfacemodel (LSM) with explicit treatment of soil moisture andevapotranspiration and an indirect soil moisture nudging schemehas been added to a mesoscale meteorology model. The new drydeposition model uses the same aerodynamic and bulk stomatalresistances computed for evapotranspiration in the LSM. Thisprovides consistent land-surface and boundary layer propertiesacross the meteorological and chemical components of the system. The coupled dry deposition model also has the advantage of beingable to respond to changing soil moisture and vegetationconditions. Modelled surface fluxes of sensible and latent heatas well as ozone dry deposition velocities were compared to twofield experiments: a soybean field in Kentucky during summer 1995and a mixed forest in the Adirondacks of New York in July 1998.(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency) (author for correspondence, e-mail(on assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency)     

Experimental Assessment of Atmospheric Ammonia Dispersion and Short Range Dry Deposition in a Maize Canopy

In order to study the effect of thevegetation structure on atmospheric ammonia(NH₃) dispersion and deposition, anexperiment was set up near Paris, in July 1997.Between 12 and 162 m downwind of a 200 m line-source releasing 600 to 1200 g NH₃hr^-1placed at the top of a maize canopy, NH₃concentration was measured, within and above thecanopy, with a set of 30 active, acid-coateddenuders over periods of 2 to 3 hr. Eight datasets were collected over a one-month period.NH₃ concentration decreased sharply withdistance to the source, from up to800 g NH₃ m^-3 at 12 m, to lessthan 10 g NH₃ m^-3 at 162 m andshowed strong vertical gradients. Within thecanopy, the concentration scaled using thefriction velocity, the canopy height, and thesource strength, exhibited a universal power lawrelationship as a function of the normaliseddownwind distance from the source. A mass balancemethod and a resistance model approach were usedas independent estimates of the cumulateddeposition at 162 m downwind from the source,which range between 1 and 29% of the emittedNH₃. Both methods agreed approximately inmagnitude. A sensitivity analysis showed that thecuticular uptake and the compensation point aremajor parameters that needs to be bettercharacterised under high NH₃ concentrationif one wants to improve NH₃ short-rangedeposition modelling.     

Model Evaluation of Dry Deposition to Vegetation for Volatile and Semi-Volatile Organic Compounds in a Multimedia Environment

Gas-phase atmospheric deposition wasevaluated in a screening level model of themultimedia environmental distribution of toxics(MEND-TOX). Algorithmic additions to MEND-TOXfor the estimation of gas-phase depositionvelocity over vegetated surfaces were analyzedusing recently published dry deposition fluxmeasurements for nitric acid. Model outputs arecompared to similar estimates from the NOAAmultilayer dry deposition model. Results of theevaluation indicate that MEND-TOX performs wellas a screening level model for the estimation ofgas-phase dry deposition velocity of nitric acidover soybeans. The present study expandsprevious laboratory results for organic speciesto include an inorganic species and open fieldand dry leaf, conditions.(On assignment to the National Exposure Research Laboratory, U.S. Environmental Protection Agency); (author for correspondence, e-mail     

PM10, O3, CO Concentrations and Elemental Analysis of Airborne Particles in a School Building

Measurements of indoor and outdoor PM10, as well as indoor O₃ and CO concentrations were conducted and are presented here. These measurements were carried out at an institute building, located in a suburban industrial area in Greece. Both indoor and outdoor PM10 samples were also collected and their elemental composition was identified by ED-XRF analysis. Twenty seven major, minor and trace elements were identified. The measurements took place generally in different periods of institute operation, from June 2004 to February 2005. The indoor PM10 concentrations which were measured during the normal operation period of the institute were found to be many times higher than the respective outdoor PM10 concentrations of the same periods. On the contrary, the indoor PM10 concentrations which were measured during the holiday period were found to be lower than their corresponding outdoor values. Indoor O₃ and CO concentrations were found to be in low level. Indoor PM10 concentrations were found to be in a relative good correlation with O₃ (r = 0.45) and in high correlation (r = 0.98) with CO concentrations. On average, total elements concentrations were much higher indoors relative to outdoors. Based on above findings we attempted to determine the pollution sources of the indoor environment and to investigate some parameters or chemical processes that affect indoor pollutants’ levels.     

ROADWAY-2: A Model for Pollutant Dispersion near Highways

The formulations and evaluation of ROADWAY-2, a near-highway pollutant dispersion model, are described. This model incorporates vehicle wake parameterizations derived from canopy flow theory and wind tunnel measurements. The atmospheric velocity and turbulence fields are adjusted to account for velocity-deficit and turbulence production in vehicle wakes. A turbulent kinetic energy closure model of the atmospheric boundary layer is used to derive the mean velocity, temperature, and turbulence profiles from input meteorological data. ROADWAY-2 has been evaluated using SF₆ tracer data from General Motors Sulfate Dispersion Experiment. The model evaluationresults are presented and discussed.     

The Effects of SO2 Pollutant on Forest Tree Needles at Mountainous Land around Izmir (Turkey)

Around the city of Izmir, Yamanlar – Manisa (north) Karabelen (south) andKemalpasa mountainous areas exist. The forested area in total covers 122,613.5 ha on these mountainous areas. This forested area has 6,146,387 m³ of wood potential. Industrial complex surroundingthe Aliaga, and thermo-electric power plants working with lignitecoal in the Soma region and some other small industrial establishmentsare located around Izmir and Manisa. These establishements have a vital importance in polluting the air. The forest, which suffers especially from SO₂ pollution, consists of Pinus brutia and Pinus nigra. Sulphur contents in 1, 2, 3 yr old needles of the trees were determined to range between 2000–8000 ppm. Microscopic investigation of the tree needles revealed that black blights on the needles indicate destruction of the cells. Annual ring thickness of trees measured showed that there has been a reduction in the forest growth and thisreduction is becoming more serious each year. Reduction in the wood production causes hundreds of billions of Turkish lira of economic loss to the Forestry Administration. It has been concluded at the end of this study that in order to stop theharm that the forests suffer, industrial establishments must pay an `ecological costs' to be added to their product cost items.     

Increase of Ozone Concentration in an Inland Basin During the Period of Nocturnal Thermal High

Since ground level ozone concentrations in the basin on one day before the occurrence of unusually high air temperature with nocturnal thermal high showed a typical urban type of a maximum ozone concentration at 1300 LST and a minimum at night. However, a maximum ozone concentration under extremely high air temperature of 39.2 °C was detected at 1700 LST or 1800 LST at two environmental monitoring sites, which was 4 or 5 hr delayed from the typical occurrence time, 1300 LST. Its maximum value showed about 50 or 70% increase of the concentration more than the typical maximum value and its concentration gradually decreased until 2100 LST. After 1200 LST until 1800 LST, air temperature was maintained over 35 °C and the high temperature made a great contribution to the increase of O₃ for several hours. The deviated occurrence time of a maximum ozone concentration is mainly attributed to meteorological and topographic effects – shifted occurrence time of maximum air temperature, shrunken atmospheric boundary layer depth and wind. While daytime O₃ concentration due to photochemical production of O₃ from NO₂ increased, NO₂ concentration decreased, with their reverse respondent patterns each night. A secondary maximum concentration of O₃ at 2300 LST or 2400 LST is due to a much shallower depth of nocturnal surface inversion layer with daytime producing more O₃ than that of the daytime convective boundary layer, resulting in the increase of ozone concentration, though the reduction of ozone occurred under the reversal process of O₃ into NO₂.     

Heterogeneous Sulfate Formation on Dust Surface and Its Dependence on Mineralogy: Balloon-Borne Observations from Balloon-Borne Measurements in The Surface Atmosphere of Beijing, China

This study focuses on providing a direct insight into the process by which sulfate is formed on mineral dust surface in the actual atmosphere. Six sets of aerosol measurements were conducted in the outskirts of Beijing, China, in 2002–2003 using a tethered balloon. The mineralogy of individual dust particles, as well as its influence on the S (sulfur) loadings was investigated by SEM-EDX analysis of the directly collected particles. The mixed layer in the urban atmosphere was found to be quite low (500–600m), often appearing as a particle dense stagnant layer above the surface. It is suggested that mineral dust is a common and important fraction of the coarse particles in Beijing (35–68%), and that it is relatively enriched with Calcite (>28%). An exceptional amount of S was detected in the mineral particles, which can be explained neither by their original composition, nor by coagulation processes between the submicron sulfates and the dust. Heterogeneous uptake of gaseous SO₂, and its subsequent oxidation on dust was suggested as the main pathway that has actually taken place in the ambient environment. The mineral class found with the largest number of particles containing S was Calcite, followed by Dolomite, Clay, Amphibole etc., Feldspar, and Quartz. Among them, Calcite and Dolomite showed distinctly higher efficiency in collecting sulfate than the other types. A positive correlation was found with the number of S containing particles and the relative humidity. Calcite in particular, since almost all of its particles was found to contain S above 60% r.h. On the other hand, the active uptake of SO₂ by the carbonates was not suggested in the free troposphere downwind, and all the mineral classes exhibited similar S content. Relative humidity in the free troposphere was suggested as the key factor controlling the SO₂ uptake among the mineral types. In terms of sulfate loadings, the relationship was not linear, but rather increased exponentially as a function of relative humidity. The humidity-dependent uptake capacity of mineral types altogether showed an intermediate value of 0.07 gSO₄ ²⁻ g⁻¹ mineral at 30% r.h. and 0.40 gSO₄ ²⁻ g⁻¹ mineral at 80%, which is fairly consistent with laboratory experiments.     

The Transit of 35SO4 2- and 3H2O Added In Situ to Soil in a Boreal Coniferous Forest

A solution containing ³⁵SO₄ ^2- and ³H₂O was applied to four plots (5 × 5 m) in a boreal coniferous forest in the Laflamme Lake watershed, Québec, under two contrasting conditions: in summer (plots 1 and 2), and on the snowpack before snowmelt (plots 3 and 4). The transit of both these tracers in the soil solution was then followed through a network of soil lysimeters located at different depths. Four months after the summer application, ³H₂O had infiltrated the whole soil profile at plot 1, while ³⁵SO₄ ^2- was only observed in the LFH and Bhf horizons. A ³⁵SO₄ ^2- budget calculated from mid-August to November indicated that 89 and 10.6% of the added ³⁵SO₄ ^2- was retained within the LFH and the Bhf layers, respectively. Fifteen months later, the added ³⁵SO₄ ^2- was distributed in the following proportions within the soil horizons: LFH (73.7%), Bhf (11.8%) and Bf (12.8%), for a total retention rate of 98.3%. The superficial penetration of ³H₂O at plot 2 was indicative of a major lateral water movement that prevented the calculation of a ³⁵SO₄ ^2- budget. This situation also was observed at plot 4 during snowmelt. At plot 3, ³H₂O moved freely through the soil profile and a significant fraction of the added ³⁵SO₄ ^2- reached the B horizons, where it was presumably adsorbed on aluminum (Al) and ferric (Fe) oxides. The ³⁵SO₄ ^2- budget for plot 3 from March to November indicated that 87% of the added ³⁵SO₄ ^2- was retained within the soil profile, with most being retained in the B horizons (LFH = 33.1%, Bhf = 33.1%, Bf = 20.8%). The contrasting retention patterns of ³⁵SO₄ ^2- within the soil profile following the summer addition and snowmelt likely was caused by the contrastingsoil temperatures and soil solution residence times within the differentsoil layers. The persistence of ³⁵SO₄ ^2- in the soil solution of the entire profile long after the initial tracer infiltration, and the relative temporal stability of specific activity of SO₄ ^2-, point to the establishment of an isotopic equilibrium between the added ³⁵SO₄ and the active S-containing reservoirs within a given soil horizon. Overall, the results clearly illustrate the very strong potential for ³⁵SO₄ ^2- retention and recycling in forest soils.     

The Influence of Atmospheric N Deposition on Nitrous Oxide and Nitric Oxide Fluxes and Soil Ammonium and Nitrate Concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO ₃ ^– and NH ₄ ⁺ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH ₄ ⁺ and NO ₃ ^– concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH ₄ ⁺ and NO ₃ ^– in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH ₄ ⁺ , but the relationship between NH ₄ ⁺ and N deposition (ln NH ₄ ⁺ = 0.62 ln N_deposition + 0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

Bioremediation of Chromate by Sulfate-Reducing Bacteria, Cytochromes c3 and hydrogenases

The treatment of soils and ground waters polluted by heavy metals is of economical and environmental interest. Reduction of Cr(VI) to the less toxic Cr(III) associated to its precipitation is a potentially useful process for bioremediation. In order to develop ecological processes using micro-organisms, we have compared various sulfate-reducing bacteria for enzymatic reduction of chromate. The best Cr(VI) reductase activity was obtained with Desulfomicrobium norvegicum. Despite morphological changes induced by the presence of chromate, this strain can grow in the presence of up to 500 M Cr(VI) and can decontaminate waters polluted by Cr(VI) when seeded in bioreactors. We have demonstrated the ability of several metalloenzymes (cytochromes c ₃ and hydrogenases) to reduce chromate. Biophysical investigations of the chromate/protein interaction in order to get further informations on the mechanism of metal reduction by cytochromes c ₃ are under the way.     

Degradation of poly(3-hydroxybutyrate), PHB,by bacteria and purification of a novel PHB depolymerase fromComamonas sp.

Bacteria capable of growing on poly(3-hydroxybutyrate), PHB, as the sole source of carbon and energy were isolated from various soils, lake water, activated sludge, and air. Although all bacteria utilized a wide variety of monomeric substrates for growth, most of the strains were restricted to degrade PHB and copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate, P(3HB-co-3HV). Five strains were also able to decompose a homopolymer of 3-hydroxyvalerate, PHV. Poly(3-hydroxyoctanoate), PHO, was not degraded by any of the isolates. One strain, which was identified asComamonas sp., was selected, and the extracellular depolymerase of this strain was purified from the medium by ammonium sulfate precipitation and by chromatography on DEAE-Sephacel and Butyl-Sepharose 4B. The purified PHB depolymerase was not a glycoprotein. The relative molecular masses of the native enzyme and of the subunits were 45,000 or 44,000, respectively. The purified enzyme hydrolyzed PHB, P(3HB-co-3HV), and—at a very low rate—also PHV. Polyhydroxyalkanoates, PHA, with six or more carbon atoms per monomer or characteristic substrates for lipases were not hydrolyzed. In contrast to the PHB depolymerases ofPseudomonas lemoignei andAlcaligenes faecalis T₁, which are sensitive toward phenylmethylsulfonyl fluoride (PMSF) and which hydrolyze PHB mainly to the dimeric and trimeric esters of 3-hydroxybutyrate, the depolymerase ofComamonas sp. was insensitive toward PMSF and hydrolyzed PHB to monomeric 3-hydroxybutyrate indicating a different mechanism of PHB hydrolysis. Furthermore, the pH optimum of the reaction catalyzed by the depolymerase ofComamonas sp. was in the alkaline range at 9.4.     

Characterization of a poly(3-hydroxybutyrate) depolymerase fromaureobacterium saperdae: Active site and kinetics of hydrolysis studies

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase was purified fromAureobacterium saperdae cultural medium by using hydrophobic interaction chromatography. The isolated enzyme was composed of a single polypeptide chain with a molecular mass of 42.7 kDa as determined by SDS-PAGE and by native gel filtration on TSK-HW-55S. The enzyme was not a glycoprotein. Its optimum activity occurred at pH 8.0 and it showed a broad pH stability, ranging from pH 3 to pH 11.N-Bromosuccinamide and 2-hydroxy-5-nitrobenzyl bromide completely inactivated the enzyme, suggesting the involvement of tryptophan residues at the active site of the protein. The enzyme was very sensitive to diisopropyl fluorophosphate and diazo-dl-norleucine methyl ester, showing the importance of serine and carboxyl groups. The modification of cysteine residues byp-hydroxy mercuricbenzoate did not cause a loss of activity, whereas dithiothreitol rapidly inactivated the enzyme, revealing the presence of disulfide bonds.A saperdae depolymerase acted on the surface layer of PHB films and the degradation proceeded by surface erosion releasing monomers and dimers of 3-hydroxybutric acid. The degradation of PHB films byA. saperdae depolymerase was partially inhibited in the presence of excess amounts of enzyme. This phenomenon, already observed by Mukaiet al. with poly(hydroxyalkanoates) depolymerases fromAlcaligenes faecalis, Pseudomonas pickettii, andComamonas testosteroni, was analyzed according to the kinetic model proposed by these authors. The experimental data evidenced a general agreement with the kinetic model, although higher initial degradation rates were found withA. saperdae depolymerase.